US4087338A - Electrowinning of nickel in diaphragm-free cells - Google Patents

Electrowinning of nickel in diaphragm-free cells Download PDF

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Publication number
US4087338A
US4087338A US05/770,472 US77047277A US4087338A US 4087338 A US4087338 A US 4087338A US 77047277 A US77047277 A US 77047277A US 4087338 A US4087338 A US 4087338A
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Prior art keywords
nickel
electrolyte
cell
electrowinning
grams per
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Expired - Lifetime
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US05/770,472
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English (en)
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Aubrey Stewart Gendron
John Ambrose
Victor Alexander Ettel
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Huntington Alloys Corp
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International Nickel Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt

Definitions

  • the present invention relates to the process of electrowinning nickel in a diaphragm-free cell.
  • Nickel is conventionally electrowon in cells wherein the cathode is isolated from the anode by a cathode box, or bag comprising a porous diaphragm which surrounds the cathode. While using such cells incorporating a diaphragm enables a relatively large nickel bite, i.e. depletion of nickel in the electrolyte on passage through the cell, to be obtained with good current efficiency, it suffers from several disadvantages.
  • the diaphragms add not only to the cost but also to the bulkiness of the cells; they necessitate the use of separate electrolyte feed-lines to each cathode, and careful handling of the cathodes to avoid tearing of the diaphragms; and by necessitating relatively low current densities they limit the speed at which electrowinning can be performed.
  • the present invention provides a process for electrowinning nickel from a chloride-free nickel-containing electrolyte in a diaphragm-free cell, wherein the electrolyte comprises an aqueous sulfate solution which contains at least about 20 gpl of a buffering agent selected from organic acids and their salts which do not precipitate nickel out of the electrolyte, are resistant to oxidizing conditions in the cell and have a dissociation pK of about 2-5 at 25° C, and wherein the electrowinning is carried out at a temperature of about 40°-60° C, the pH of the electrolyte within the cell being maintained at about 2.5-4.5 while the relative flow rates of electrolyte into and out of the cell are selected to maintain a substantially constant volume of electrolyte within the cell and to cause the nickel concentration in the electrolyte to be depleted by at least about 5 gpl on passage through the cell.
  • the electrolyte comprises an aqueous sulfate solution which contains at least about 20 g
  • An essential ingredient in the electrolyte used in the process of the invention is an effective buffering agent.
  • the latter needs to possess not only adequate buffering ability, but also adequate buffering capacity, so that if a sufficient amount of the agent is present in the electrolyte, the pH of the latter can be maintained in the desired range of 2.5-4.5 despite the formation of substantial quantities, e.g., 15 gpl or more, of acid during the electrowinning operation.
  • bisulfate ions do not serve as an effective buffering agent due to their inability to buffer at pH values in excess of 2.
  • boric acid though it may be present in the electrolyte, will not serve as an effective buffering agent because it lacks the buffering capability at pH values lower than 5 and moreover lacks the buffering capacity to cope with substantial amounts of acid formed.
  • buffering agents organic acids such as acetic, propionic, butyric, succinic and citric acids as well as various salts of these acids are particularly useful as buffering agents in the process of the invention.
  • Other considerations which may influence the choice or preference of buffering agent include, for example, the vapor pressure which will be exerted by the agent in question at the cell temperature.
  • the buffering agent used must be present in an amount of at least 20 gpl, and preferably at least 50 gpl.
  • the electrolyte composition and its flow rates into and out of the cell, the current density used as well as the temperature at which the cell is maintained are correlated to achieve the desired nickel bite.
  • electrolyte having a pH of about 5-6 measured at room temperature is treated in a diaphragm-free cell maintained at 55° C.
  • the flow rate it is possible to achieve nickel bites of 10 gpl or more with good current efficiency. The latter decreases generally with increasing nickel bite, but can be of the order of 75% or more when the nickel bite is of the order of 10 gpl.
  • the cell is operated at 50°-55° C and the pH in the cell measured at operating temperature, is maintained within the range of 3-4.
  • the pregnant electrolyte introduced into the cell preferably has a pH of about 5-6 measured at room temperature and contains about 40-130 gpl of nickel.
  • the electrolyte may also include reagents which improve the conductivity thereof, or the appearance of the deposited nickel.
  • sodium sulfate in an amount up to 75 gpl, and magnesium sulfate in an amount of 0.5 gpl or more may be present in the electrolyte.
  • the process of the invention can be practised by using a wide range of current densities, e.g., as low as 50 or as high as 1500 amperes per square meter of cathode; it is generally preferred to employ a current density of 300-1000 amperes per square meter of cathode.
  • the cells used in the process of the invention are relatively compact with anode to cathode spacings of the order of 2.5-5 centimeters. As a result of using such small spacings, the power requirements are considerably reduced and are comparable to those prevailing in conventional cells using much lower current densities.
  • the electrodes used in practising the process of the invention may be any of the wide variety of known electrodes for nickel electrowinning.
  • the anode may comprise a titanium sheet coated with a noble metal
  • the cathode may comprise a nickel starter sheet, or a sheet of stainless steel or titanium suitably treated to give the desired degree of adhesion to the deposit.
  • FIG. 1 shows the variation of nickel bite obtained with the operating pH maintained in the cell, as measured at the cell temperature, in the tests of Example 1 below;
  • FIG. 2 shows the current efficiency, calculated from the cell voltage and current and the weight of deposited nickel, as a function of the operating pH in the tests of Example 1;
  • FIG. 3 represents the same data in form of a plot of the current efficiency as a function of the nickel bite.
  • a series of electrowinning tests were performed using an electrolyte comprising 85 gpl of nickel as nickel sulfate, 75 gpl of sodium acetate (CH 3 COONa. 3H 2 O), 75 gpl of sodium sulfate and 5 gpl of magnesium sulfate.
  • a diaphragm-free cell was used in which the anode consisted of a commercial dimensionally stabilized anode sheet having a surface area of 0.64 square decimeters, and the cathode consisted of a nickel starter sheet having a surface area of 1 dm 2 and spaced from the anode by 2.5 cm.
  • the electrolyte was introduced into the cell at a pH, measured at room temperature, of 5.5.
  • the electrolyte within the cell was maintained at 55 ⁇ 2° C while electrowinning was carried out with the current density controlled at 500 amp/m 2 .
  • the tests were performed for deposition periods ranging from 30 seconds to 40 minutes, and the results obtained are illustrated in the graphs of FIGS. 1-3 of the accompany drawings.
  • the electrolyte used was of the same composition as in Example 1.
  • the cell used in this case differed in that the cathode was a sandblasted titanium sheet with a surface area of 0.32 dm 2 .
  • the test was performed, at 55 ⁇ 2° C, with a 1000 amp/m 2 cathodic current density (the cell voltage being 2.78 volts) for a 24 hour duration.
  • the flow rates of electrolyte into and out of the cell were selected to maintain an operating pH of about 3.5 and obtain a nickel bite of 10 gpl.
  • the calculated current efficiency was 83%.
  • no visual evidence of decomposition of the organic buffering agent at the anode was detected.
  • Example 2 Using the same solution and cell as in Example 2, a test was performed using a lower cell voltage (2.6 volts) to maintain a cathodic current density of 650 amp/m 2 . The flow rates in this case were controlled to maintain an operating pH of about 3 at 55 ⁇ 2° C. The resulting nickel bite and current efficiency were found to be 13.5 gpl and 75% respectively.
  • the pregnant electrolyte was fed into the cell at a room temperature pH of about 6.
  • the cell voltage of 2.5 volts was selected to give a cathodic current density of 300 amp/m 2 , and the flow rates were controlled to maintain a pH of about 4 in the cell, as measured at the operating temperature (55 ⁇ 2° C).
  • the resulting nickel deposit was found, as in the previous examples, to be bright and pit free, and the nickel bite and current efficiency were found to be 10 gpl and 80%, respectively.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US05/770,472 1976-05-27 1977-02-22 Electrowinning of nickel in diaphragm-free cells Expired - Lifetime US4087338A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA253,463A CA1062652A (en) 1976-05-27 1976-05-27 Electrowinning of nickel in diaphragm-free cells
CA253463 1976-05-27

Publications (1)

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US4087338A true US4087338A (en) 1978-05-02

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US (1) US4087338A (fi)
JP (1) JPS52144320A (fi)
AU (1) AU2484377A (fi)
CA (1) CA1062652A (fi)
FI (1) FI771514A (fi)
FR (1) FR2352896A1 (fi)
NO (1) NO771814L (fi)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012024052A1 (en) * 2010-08-18 2012-02-23 Macdermid, Incorporated NICKEL pH ADJUSTMENT METHOD AND APPARATUS

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1754125A (en) * 1928-03-30 1930-04-08 Smith Stanley Cochran Electrolytic recovery of metals
JPS4218205Y1 (fi) * 1964-07-16 1967-10-21
CA895500A (en) * 1972-03-14 Kewanee Oil Company High speed electrodeposition of nickel
US3743585A (en) * 1971-10-12 1973-07-03 Sec Corp Metal recovery process
US3928153A (en) * 1974-04-09 1975-12-23 Int Nickel Co Electrowinning process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA895500A (en) * 1972-03-14 Kewanee Oil Company High speed electrodeposition of nickel
US1754125A (en) * 1928-03-30 1930-04-08 Smith Stanley Cochran Electrolytic recovery of metals
JPS4218205Y1 (fi) * 1964-07-16 1967-10-21
US3743585A (en) * 1971-10-12 1973-07-03 Sec Corp Metal recovery process
US3928153A (en) * 1974-04-09 1975-12-23 Int Nickel Co Electrowinning process

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Plating and Surface Finishing, vol. 62, pp. 865-869, 1975. *
Proceedings of the 14th Electrochemical Seminar, pp. 16-28, 1973. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012024052A1 (en) * 2010-08-18 2012-02-23 Macdermid, Incorporated NICKEL pH ADJUSTMENT METHOD AND APPARATUS
CN103108995A (zh) * 2010-08-18 2013-05-15 麦克德米德股份有限公司 镍pH值调整方法及设备
TWI451003B (zh) * 2010-08-18 2014-09-01 Macdermid Inc 鎳ｐｈ值調整方法及設備
US8980068B2 (en) 2010-08-18 2015-03-17 Allen R. Hayes Nickel pH adjustment method and apparatus
CN103108995B (zh) * 2010-08-18 2015-12-16 麦克德米德股份有限公司 镍pH值调整方法及设备

Also Published As

Publication number Publication date
FI771514A (fi) 1977-11-28
AU2484377A (en) 1978-11-09
CA1062652A (en) 1979-09-18
JPS52144320A (en) 1977-12-01
NO771814L (no) 1977-11-29
FR2352896A1 (fr) 1977-12-23

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